CN103930518A - Luminescent material and a process of forming the same - Google Patents

Luminescent material and a process of forming the same Download PDF

Info

Publication number
CN103930518A
CN103930518A CN201280055332.9A CN201280055332A CN103930518A CN 103930518 A CN103930518 A CN 103930518A CN 201280055332 A CN201280055332 A CN 201280055332A CN 103930518 A CN103930518 A CN 103930518A
Authority
CN
China
Prior art keywords
luminescent material
approximately
weighting agent
room
volume
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201280055332.9A
Other languages
Chinese (zh)
Other versions
CN103930518B (en
Inventor
V·奥斯本斯基
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Luxim Solutions LLC
Original Assignee
Saint Gobain Industrial Ceramics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Industrial Ceramics Inc filed Critical Saint Gobain Industrial Ceramics Inc
Publication of CN103930518A publication Critical patent/CN103930518A/en
Application granted granted Critical
Publication of CN103930518B publication Critical patent/CN103930518B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/77742—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7787—Oxides
    • C09K11/7789—Oxysulfides

Abstract

A luminescent material can be formed by a process using a vacancy-filling agent that includes vacancy-filling atoms. In an embodiment, the process can include forming a mixture of a constituent corresponding to the luminescent material and the vacancy-filling agent. The process can further include forming the luminescent material from the mixture, wherein the luminescent material includes at least some of the vacancy-filling atoms from the vacancy-filling agent. In another embodiment, the process can include melting a constituent corresponding to the luminescent material to form a melt and adding a vacancy-filling agent into the melt. The process can also include forming the luminescent material from the melt, wherein the luminescent material includes at least some of the vacancy-filling atoms from the vacancy-filling agent. The luminescent material may have one or more improved performance properties as compared to a corresponding base material of the luminescent material.

Description

Luminescent material and forming method thereof
Technical field
The disclosure relates to luminescent material, their formation method and the device with scintillator, and described scintillator has such compound.
Background technology
Scintillator can be used for medical imaging and in oil and gas industry for well logging and for environmental monitoring, safety applications, and for nuclear physics analysis and application.Scintillator comprises luminescent material, and described luminescent material comprises rare earth element, at compound rare earth elements, can be wherein doping agent or as main ingredient.The further improvement of luminescent material is desired.
Accompanying drawing explanation
By means of embodiment, describe embodiment, and embodiment is not limited to accompanying drawing.
Fig. 1 comprises the explanation of device, and described device comprises the scintillator having according to the luminescent material of an embodiment.
Those skilled in the art will appreciate that element in figure is by for simple and object and illustrating clearly, and there is no need it to draw to scale.For example, the size of some element in figure can be amplified with respect to other elements, to help improve the understanding to embodiment of the present invention.
Specific embodiments
Below in conjunction with illustrated description, be provided for helping to understand instruction disclosed herein.Discussion below will concentrate in the specific implementation and embodiment of instruction.Thisly emphasize to be provided for help to describe instruction, and should not be interpreted as the scope of instruction or the restriction of applicability.
Before proposing following embodiment details, first define or illustrate some terms.Corresponding to the family's sequence number being listed as in the periodic table of elements, use referring to " CRC Handbook ofChemistry and Physics ", " rebaptism method " pact described in the 81st edition (2000).
As used in this specification sheets, color space represents according to L*, a* and b* coordinate as clear and definite in International Commission on Illumination (" CIE ") 1976.(L*=0 produces black and L*=100 represents diffusion white for the lightness of these three coordinate representation colors; Minute surface white can be higher), its position between redness/magneta colour and green (a*, negative value represents green, and on the occasion of representing magneta colour) and its position (b*, negative value represents blueness and yellow on the occasion of representing) between yellow and blueness.
Unless expressly stated otherwise,, boiling provided herein and sublimation temperature are under a barometric point (about 101kPa, absolute pressure).
Term " compound " is intended to refer to a plurality of similar molecules substantially.When formation comprises the crystal ingot of monocrystalline substantially, crystal ingot can have single compound, even because partition coefficient molecular formula can be along the length slight change of crystal ingot, so molecular formula is not uniformly perfect along the length of crystal ingot.Term " material " is intended to refer to a kind of composition, form no matter, and it comprises compound and is not potential atom or the molecule of a part for this compound.Such atom or molecule can be arranged in the interstitial site of the matrix of compound, or can be dissolved in material.
During element-specific in mentioning compound, letter ' M ' is intended to refer to metallic element.For example, M 2+for representing divalent metal.M 3+be for representing trivalent metal, in one embodiment, it can be rare earth element, and in another embodiment, it can be the trivalent metal except rare earth element, such as Al, Ga, Sc, In etc.
During element-specific in mentioning compound, term " main ingredient " is intended to refer to that element exists as a part for compound molecule formula rather than as doping agent.Doping agent in compound exists to be not more than the concentration of 5% atom conventionally.As an example, mix the LaBr of Ce 3(LaBr 3: Ce) comprise that La and Br are as main ingredient, and Ce is doping agent rather than main ingredient.
Term " rare earth " or " rare earth element " are intended to refer to the lanthanon (Ce to Lu) in Y, Sc, La and the periodic table of elements.In chemical formula, rare earth element is expressed as " RE ".
As used herein, term " comprises (comprises) ", " having comprised (comprising) ", " comprising (includes) ", " having comprised (including) ", " having (has) ", " (having) that have " or their any other distortion are all intended to cover comprising of a kind of nonexcludability.For example, comprise that a kind of technique, method, article or the device of a row feature not necessarily only limits to those features, but can comprise for this technique, method, article or install and clearly do not list or other intrinsic features.In addition, unless on opposite meaning clearly statement, " or " refer to a kind of inclusive or rather than a kind of exclusiveness or.For example, it is that true (or existence) and B are false (or not existing) that condition A or B meet with lower any one: A, and A is that false (or not existing) and B are true (or existence), and A and B both true (or existence).
Use " a kind of/mono-" (a/an) to describe key element described herein and integral part.Do is like this only in order to facilitate and provide a kind of generality meaning of the scope of the invention.Unless clear, refer to other situations, otherwise this specification sheets should be read as and comprise one or at least one, and odd number also comprises plural number, or vice versa.
Unless otherwise defined, all technical and scientific term has the identical meaning as conventionally understood those skilled in the art as used herein.These materials, method and example are only illustrative and and are not intended to be limited.With regard to the scope in this unexplained reference, about many details of concrete material and processing behavior, be conventional and can in other starting material within textbook and flicker and radiation detection field, find.
Can form luminescent material with room weighting agent, described room weighting agent can help in forming process, room to be filled atom and introduce in luminescent material, rather than only relies on luminescent material environment around to provide room to fill atom.From luminescent material environment diffusion room around, fill atom and compare with only relying on, in the use that forms luminescent material Vacancy weighting agent, reducing in the possibility that forms room in finished product luminescent material substantially more effective.For containing the luminescent material of rare earth, the use of room weighting agent can be useful especially, because such luminescent material is relatively fine and close and has relatively low spread coefficient.Room weighting agent can be used and be not limited to only with together with the luminescent material of rare earth to use together with other luminescent materials.
Compare with the corresponding luminescent material when room weighting agent not being incorporated in melt or body in forming process, the luminescent material that uses room weighting agent to form can have higher light output, lower energy resolution, lower twilight sunset, better ratio, shorter fall time or its arbitrary combination.
The luminescent material that the method for using room weighting agent to form luminescent material can start from based on desired formation is selected room weighting agent.Room weighting agent can provide O, S or X atom, and wherein X is halogen.Room weighting agent can be the compound that comprises room filling atom and other atoms, and described other atoms comprise the element different from the element of room filling atom.Other atoms are conventionally different from any atom in the matrix of luminophor in luminescent material.Other atoms can comprise the most atoms metal of other atoms of the main ingredient in luminophor of chemical bonding not.In a specific embodiment, atoms metal comprises Ba, Sn, Zn, Zr, Hf, Cd, Pb or its arbitrary combination.In finished product luminescent material, luminescent material can not basically contain any other atom, or at luminescent material, comprises the degree of other atoms, and other such atoms can only be present in interstitial site and not in the matrix of luminophor.In another embodiment, room weighting agent can comprise that room fills atom and do not comprise any other atom, and the example of such room weighting agent comprises sulphur.
The amount of can the total mass based on parent material determining room weighting agent.For specific luminophor, under low concentration, the improvement of performance can become significantly and performance can be improved along with the increase of concentration.In a specific embodiment, within the scope of finite concentration, performance can be the linear function of concentration.Under higher concentration, can the become further increase of saturated and concentration of performance does not further significantly improve performance.As an example, mix cerium lutetium yttrium orthosilicate (LYSO:Ce) and in the concentration of 0.1 % by weight, start can start to demonstrate the remarkable improvement of performance, and improve and can linearity be increased at least 0.5 % by weight.In 1.0 % by weight or 2 % by weight, along with the increase of concentration, may not can observe further and significantly improve.For mixing cerium lanthanum bromide (LaBr 3: Ce), the respective concentration of room weighting agent can be less than the concentration for LYSO:Ce.LaBr 3: Ce starts can start to demonstrate the remarkable improvement of performance in the concentration of 0.001 % by weight, and improves and can linearity be increased to 0.01 % by weight.In 0.01 % by weight, along with the increase of concentration, may not can observe further and significantly improve.
In one embodiment, room weighting agent be form luminescent material parent material total mass at least about 0.0002 % by weight, at least about 0.001 % by weight, at least about 0.002 % by weight, at least about 0.02 % by weight, at least about 0.05 % by weight, at least about 0.11 % by weight or at least about 0.3 % by weight.In another embodiment, room weighting agent is being not more than approximately 50 % by weight, being not more than approximately 20 % by weight, being not more than approximately 9 % by weight, being not more than approximately 5 % by weight, being not more than approximately 2 % by weight, being not more than approximately 0.7 % by weight, being not more than approximately 0.2 % by weight, being not more than approximately 0.09 % by weight, being not more than approximately 0.02 % by weight or being not more than 0.01 % by weight of total mass that forms the parent material of luminescent material.
Room weighting agent for example, can be solid and make can more easily process with gas and liquid phase ratio under room temperature (, approximately 20 ℃).Any other parent material that can be similar to for luminescent material adds room weighting agent.Therefore, compare with other parent material, the use of room weighting agent does not need significantly different processing or devices.Therefore, to existing apparatus setting or technical process need not modify or only with making very little modification.In another embodiment, if needed or expectation, room weighting agent can be liquid or gaseous phase.Before melt composition, room weighting agent can be a part for material blends, can after forming melt, add or can before sintering body, be incorporated into body.Some considerations about vaporization temperature have below been described.Vaporization temperature under mineralization pressure can refer to sublimation point or the boiling point of room weighting agent.Many rooms weighting agent can distil, and other room weighting agents can become liquid phase from solid phase before boiling.Can or approach under normal atmosphere from the many luminescent materials of melt composition at normal atmosphere.Can under substantially higher than atmospheric pressure, use sintering step to form other luminescent materials.Therefore, at normal atmosphere or approach the room weighting agent that may not be suitable for forming under normal atmosphere and can be suitable for forming under higher pressure, because the vaporization temperature of room weighting agent is because pressure increase can be higher.
The vaporization temperature of room weighting agent can be in approximately 250 ℃ of the temperature of fusion of luminescent material.In another embodiment, the vaporization temperature of room weighting agent can approximately 200 ℃ of the temperature of fusion of luminescent material with interior, approximately 150 ℃ with interior, approximately 90 ℃ with interior, approximately 50 ℃ with interior or approximately 20 ℃ in.In one embodiment, room weighting agent has the vaporization temperature higher than the temperature of fusion of luminescent material.In a specific embodiment, the vaporization temperature of room weighting agent than the temperature of fusion of luminescent material high at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.In another embodiment, room weighting agent has the vaporization temperature lower than the temperature of fusion of luminescent material.In a specific embodiment, the vaporization temperature of room weighting agent than the temperature of fusion of luminescent material low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.In another embodiment, the vaporization temperature of room weighting agent can be than the temperature of fusion of luminescent material larger about 250 ℃.
Luminescent material can be the form of using the ceramic body of sintering operation formation under sintering temperature and sintering pressure.Under sintering pressure, the vaporization temperature of room weighting agent can be in approximately 250 ℃ of sintering temperature.In another embodiment, under sintering pressure the vaporization temperature of room weighting agent can approximately 200 ℃ of sintering temperature with interior, approximately 150 ℃ with interior, approximately 90 ℃ with interior, approximately 50 ℃ with interior or approximately 20 ℃ in.In one embodiment, room weighting agent has the vaporization temperature lower than sintering temperature.In a specific embodiment, under sintering pressure the vaporization temperature of room weighting agent than sintering temperature low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.In another embodiment, the vaporization temperature of room weighting agent can be than sintering temperature larger about 250 ℃.
Before forming melt or body, can be by room weighting agent with the combination of components corresponding to luminescent material to form mixture.In another embodiment, can form melt and room weighting agent can be added into melt from this component.In another embodiment, in treating processes, can add room weighting agent in a plurality of different time.In one embodiment, room weighting agent is single kind of room weighting agent, and in another embodiment, room weighting agent is multiple room weighting agent.In another embodiment, component is that (for example, component can be LaBr to single kind of component 3powder), and corresponding luminescent material be LaBr substantially 3monocrystalline, and in another embodiment, component is various ingredients.Can adjust the quantity of room weighting agent and the quantity of component according to the needs of application-specific or expectation, and about when by the moment of room weighting agent and component or melt combination.
The selection of room weighting agent can be depended on the luminescent material of formation.Can use can be in response to any material of electromagnetic radiation, ionic fluid or pulse or electron beam or impulse ejection light.Compare with the material with the possibility etc. in relatively high spread coefficient, relatively low density, relatively little formation room, for the material with the possibility etc. in relatively low spread coefficient, relatively high density, relatively large formation room, room weighting agent can have impact more significantly.Conventionally, rare earth compound particularly has more rather than those of atom still less in molecule, can be significantly favourable by the use of room weighting agent.
Luminophor can be oxygenatedchemicals.In embodiments, exemplary compounds comprises: Ba 2mgSi 2o 7, Ba 2si 3o 8, Ba 2siO, Ba 2znSi 2o 7, Ba 5si 8o 21, BaSi 2o 5, BaSiO 3, Gd 2si 2o 7, Li 2caSiO 4, Lu (2-2x)gd (2x)siO 5, Lu (2-2x)y 2xsiO 5, Lu 2si 2o 7, MgSr 2si 2o 7, NaLaSiO 4, Y 2siO 5deng, wherein each x, y and z can be 0 to 1 scopes.In another embodiment, exemplary compounds can comprise: BaAl 10mgO 17, BaAl 12o 19, BaHfO 3, CaHfO 3, Gd 2o 3, Gd 3sc 2al 3o 12, Gd 3y 3al 10o 24, La 2o 3, LaAlO 3, SrHfO 3, YAlO 3, Lu (1-x)y xalO 3, (Lu (1-x-z)gd xy z) 3(Al (1-y)ga y) 5o 12deng, wherein each x, y and z can be 0 to 1 scopes.In another embodiment, exemplary compounds comprises: Ba 2b 5o 9cl, Ba 2ca (BO 3) 2, Ba 3gd (BO3) 3, Ca 4yO (BO 3) 3, CaLaB 7o 13, CaYBO 4, GdB 3o 6, GdBO 3, LaB 3o 6, LaBO 3, LaMgB 5o 10, Li 6gd (BO 3) 3, Li 6y (BO 3) 3, LuBO 3, ScBO 3, YAl 3b 4o 12, YBO 3deng.In another embodiment, exemplary compounds comprises: AgGd (PO 3) 4, Ba 2p 2o 7, Ba 3(PO 4) 2, Ba 3b (PO 4) 3, Ba 3p 4o 13, Ba 5(PO 4) 3f, BaKPO 4, BaP 2o 6, Ca 5(PO 4) 3f, CaBPO 5, CeP 5o 14, CsGd (PO 3) 4, CsLuP 2o 7, CsYP 2o 7, K 3lu (PO 4) 2, KGd (PO 3) 4, LuP 2o 7, KYP 2o 7, LiCaPO 4, LiGd (PO 3) 4, LuPO 4, NaBaPO 4, NaGd (PO 3) 4, NaLuP 2o 7, RbLuP 2o 7, RbYP 2o 7, Sr 5(PO 4) 3f etc.Each aforesaid compound can comprise the rare earth dopant that chemical formula is not provided.
Luminophor can be halogen contained compound.In one embodiment, exemplary compounds comprises: Ba 2gdCl 7, Ba 2yCl 7, BaBr 2, BaBrI, BaCl 2, BaF 2, BaGdCl 5, BaI 2, BaY 2f 8, BiF 3, CaF 2, CaI 2, Cs 2liCeCl 6, Cs 2liLuCl 6, Cs 2liYBr 6, Cs 2liYCl 6, Cs 2naLaBr 6, Cs 2naLuBr 6, Cs 2naYBr 6, Cs 3ceCl 6, Cs 3gd 2i 9, Cs 3laBr 6, Cs 3lu 2i 9, Cs 3luI 6, CsBa 2i 5, CsCe 2cl 7, CsGd 2f 7, CsI, CsY 2f 7, GdBr 3, GdCl 3, K 2ceBr 5, K 2laCl 5, K 2yF 5, KLu 2f 7, KLuF 4, KYF 4, La (l-x)ce xbr 3, LaCeF 6, La (l-x)ce xcl 3, LaF 3, LaI 3, Li 3yCl 6, LiI, Lu (l-x)gd xi 3, Lu (l-x)y xi 3, LuBr 3, LuCl 3, LuI 3, PbCl 2, PrBr 3, PrF 3, Rb 2ceBr 5, LiCaAlF 6, Rb 2liYBr 6, RbGd 2br 7, SrBr 2, SrF 2, SrI 2, YCl 3deng, wherein x can be 0 to 1 scope.
Luminophor can be sulfocompound.In one embodiment, exemplary compounds comprises: Gd 2s 3, Lu 2s 3deng.
Luminophor can comprise a more than negatively charged ion that can produce room, such as metal oxygen halogenide, metal oxygen sulfide etc.In one embodiment, an exemplary, luminophor comprises: Gd 2o 2s, La 2o 2s etc.
Each aforementioned luminophor can comprise the rare earth dopant that chemical formula is not provided.Rare earth dopant can be single valence (for example, RE 3+) or mixture (for example, the RE of valence state 3+/ RE 4+or RE 2+/ RE 3+).
Herein disclosed is many luminescent materials and be for operable luminescent material is described, rather than restriction.After reading this specification sheets, it should be appreciated by those skilled in the art that and can use other luminescent materials, wherein other such luminescent materials comprise that rare earth element is as main ingredient or as doping agent.
After determining luminescent material, the selection that negatively charged ion that can be based in luminophor and formation technology are determined room weighting agent.Negatively charged ion can be O, S, X (wherein X is halogen) or its combination, such as oxysulfide or oxyhalogenation thing.Room weighting agent for melting process was resolved before the room weighting agent for sintering process.
In one embodiment, luminescent material comprises oxygenatedchemicals, such as metal-silicon-oxygen compound, metal-boron-nitrogen compound, metal-aluminium-oxygen compound, metal-phosphorus-oxygen compound, metal-oxygen-sulphur compound, metal-oxygen-halogen compounds etc.In a specific embodiment, the metallic element in this compounds can be rare earth element.Room weighting agent can comprise metal oxide.In a more specific embodiment, room weighting agent can be BaO or with barium peroxide BaO 2(at 450 ℃, be decomposed into BaO and O 2) form, SnO 2, ZnO or its arbitrary combination.The boiling point of barium is approximately 1870 ℃, and the boiling point of BaO is approximately 2000 ℃.The boiling point of tin is approximately 2600 ℃, SnO 2sublimation point be approximately 1900 ℃.The boiling point of zinc is approximately 907 ℃, and ZnO decomposes at the temperature of approximately 1975 ℃.When luminescent material comprises containing compound such as the rare earth silicate of rare earth-oxygen, rare earth aluminate uhligite, rare earth aluminium garnet etc., such oxide compound can be useful.The fusing point of such rare earth-oxygen compound can be in the scope of approximately 1800 ℃ to approximately 2200 ℃.
In another embodiment, luminescent material comprises halogen contained compound, such as metal halide, metal-oxygen-halogen compounds etc.In a specific embodiment, the metallic element in this compounds can be rare earth element.Room weighting agent can comprise metal or ammonium halogenide.In a more specific embodiment, room weighting agent can be ZnX 2, ZrX 4, HfX 4, NH 4x, SnX 2or its arbitrary combination, wherein X is halogenide.For example, room weighting agent can be metal bromide, such as ZnBr 2, ZrBr 4or HfBr 4.The boiling point of zinc is approximately 907 ℃, ZnBr 2boiling point be approximately 650 ℃.The boiling point of zirconium is approximately 4377 ℃, ZrBr 4sublimation point be approximately 375 ℃.The boiling point of hafnium is approximately 4602 ℃, HfBr 4sublimation point be approximately 420 ℃.NH 4br and NH 4the sublimation point of I is approximately 452 ℃ and approximately 551 ℃ respectively.When luminescent material comprises that such halogenide can be useful containing compound such as the rare earth halide of rare earth-halogen, rare earth oxyhalogenation thing etc.The fusing point of such rare earth-halogen compounds can be in the scope of approximately 500 ℃ to approximately 1000 ℃.
In another embodiment, luminescent material comprises sulfocompound, such as metal sulphide compound, metal-oxygen-sulphur compound etc.In a specific embodiment, the metallic element in this compounds can be rare earth element.Room weighting agent can comprise metallic sulfide or sulphur.In a more specific embodiment, room weighting agent can be CdS, PbS 2, S or its arbitrary combination.The boiling point of cadmium is approximately 765 ℃, and the sublimation point of CdS is approximately 980 ℃.Plumbous boiling point is approximately 1740 ℃, and the boiling point of PbS is 1280 ℃.The boiling point of sulphur is approximately 445 ℃.When luminescent material comprises containing compound such as the rare-earth sulfide of rare earth-sulphur, rare earth oxysulfide etc., such sulphurous materials can be useful.
Can form luminescent material with sintering technology.Can be under atmospheric pressure or under atmospheric pressure, carry out sintering being significantly higher than.When pressure increases, compound has higher vaporization temperature conventionally.The selection of room weighting agent will depend on that body is by the temperature and pressure being exposed.In one embodiment, can use many aforesaid rooms weighting agent, and in another embodiment, can use other room weighting agents all as described below those.In another embodiment, can also use and other room weighting agents.After reading this specification sheets, those skilled in the art can be for specific process choosing room weighting agent be to form the ceramic body of luminescent material.
After selecting component and room weighting agent, processing sequence can depend on specific process (process or sintering process based on fusing) and formed specific luminescent material.
In one embodiment, the powder of component and room weighting agent can be mixed to form mixture.Component can be one or more oxide compounds, halogenide, sulfide or its combination.For example, mix the Luetcium aluminum garnet of cerium, this component can comprise CeO 2, Lu 2o 3and Al 2o 3.Room weighting agent can comprise that BaO is (or with BaO 2form), SnO 2, ZnO is (or with ZnO 2form) or its arbitrary combination.Mix cerium lanthanum bromide and can there is the CeBr of comprising 3and LaBr 3component.Room weighting agent can comprise ZnBr 2, ZrBr 4, HfBr 4, NH 4x, SnBr 2or its arbitrary combination.The oxygen gadolinium sulfide of mixing europium can have the Eu of comprising 2o 2s and Gd 2o 2the component of S.Room weighting agent can comprise CdS, PbS 2, S or its arbitrary combination.Between these components, those skilled in the art can determine the suitable component usage quantity for the specific luminophor that will form.
In the specific process based on melt, the mixture of powder can be put into crucible.In an optional embodiment, first powder can be mixed in crucible.By the powder heating of crucible and mixing.Heating sequence and time can depend on the vaporization temperature of room weighting agent be higher than or lower than the temperature of fusion of luminescent material and vaporization and temperature of fusion, be to have to approach each other more.Heating sequence can help room weighting agent to produce room filling atom and in the luminophor of luminescent material, form the possibility in room to reduce at least partly.If there is other atoms in the weighting agent of room, other such atoms can be used as steam and are removed, such as Zn or Sn.For such room weighting agent, there is no that other atoms can be incorporated into luminescent material particularly in the matrix of luminophor.In another embodiment, some other atoms possibly cannot be completely removed as steam, such as Ba, and can in luminescent material, exist; Yet such atom may reside in interstitial site and there is no that such atom can be incorporated in the matrix of luminophor.Other atoms are as steam, to be removed or can to depend on the particular combination of room weighting agent and luminophor in luminescent material.
In one embodiment, the vaporization temperature of room weighting agent than the temperature of fusion of luminophor low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.If vaporization temperature during lower than temperature of fusion and in approximately 80 ℃ of temperature of fusion, just can be taken mixture to the temperature of fusion of luminophor without any special preventive measures.If vaporization temperature than temperature of fusion larger about 100 ℃, mixture can be taken to the approximately vaporization temperature of room packing material, and before mixture being taken to another temperature of the temperature of fusion that approaches luminescent material, mixture can be remained at such temperature at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.Such heating operation can help prevent room weighting agent to volatilize under too high speed, and it may cause mixture to spill crucible.Mixture can be taken to another temperature of the temperature of fusion that approaches luminescent material.
In another embodiment, the vaporization temperature of room weighting agent is higher than the temperature of fusion of luminophor.In a specific embodiment, vaporization temperature than temperature of fusion high at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.This process can comprise heated mixt, comprises mixture is heated to at least vaporization temperature of room weighting agent.Mixture can be under vaporization temperature or higher temperature at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.After heated mixt, this process may further include another temperature that mixture is cooled to approach the temperature of fusion of luminophor.
In aforementioned any embodiment, mixture can be remained on the temperature of fusion that is close to or higher than luminescent material at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.The component of luminophor can react each other, the matrix of doping luminophor.
In another embodiment, if make room weighting agent be exposed to component or luminophor or continue the long time at specific temperature, it can form separated phase.For example, mix cerium lutetium yttrium orthosilicate and can there is the CeO of comprising 2, Lu 2o 3, Y 2o 3and SiO 2component.Room weighting agent can comprise BaO, SnO 2, ZnO or its arbitrary combination.If component and room weighting agent are mixed under about room temperature, be then heated to mix the fusing point of cerium lutetium yttrium orthosilicate, can form separated phase.In order to reduce the possibility that forms separated phase, can form melt from the mixture of component.Room weighting agent can be added into melt.Other combinations of luminophor and room weighting agent can be affected similarly, and can mix and the time interpolation room weighting agent after heat contents first.
In another embodiment, can use sintering process.For the component of luminophor and room weighting agent, it can be the form of powder and as described earlier mixed.Can add tackiness agent to help the formation of body; But, can not need tackiness agent.Can be by the shape for body that is combined to form of powder and tackiness agent.If do not use tackiness agent, powder can be placed in to the container that defines body shape.Alternatively, powder can be pressed into the shape of body.
Body can be placed in to agglomerating plant.If there is tackiness agent in body, can be less than 500 ℃ such as approximately 200 ℃ at the temperature in the scope of 300 ℃ by tackiness agent burn off.Can under about normal atmosphere, in well-oxygenated environment, carry out burn off.Can use other conditions to remove tackiness agent.Obviously, if there is no tackiness agent can omit tackiness agent burn off.
Can body be heated to sintering temperature with agglomerating plant or approach the temperature of sintering temperature.Pressure in device can be at normal atmosphere to the scope of sintering pressure, or can be brought to normal atmosphere to the scope of sintering pressure.Can selective pressure make the vaporization temperature of room weighting agent under such pressure be not more than approximately 250 ℃ than sintering temperature is low.In a specific embodiment, the vaporization temperature of room weighting agent under this pressure than sintering temperature low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.In a specific embodiment, the vaporization temperature under this pressure can be about sintering temperature.Room weighting agent can distil or decompose and not for example, to body have a negative impact (, fracture or broken body).Can keep temperature and pressure at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.Identical or other conditions can be used for to different luminophors or use another room weighting agent.Distillation or the decomposition that should control room weighting agent make not damage body in distillation or decomposition course.Then body can be taken to sintering pressure to complete the formation of the luminescent material of ceramic body form.
In another embodiment, luminescent material can be monocrystalline form or as polycrystalline material.Can use fusion area method, crystal pulling method (Czochralski), Bridgman method (Bridgman) or guided mode method (edge defined film-fed growth (EFG) technique) to form the luminescent material of monocrystalline form.For fusion area method, can process the end in contact that solid material makes seed crystal and solid, and thermal source causes near the fusing that becomes of regional area (part solid) crystal.For example, for LYSO, near the envrionment temperature material of fusing can be at least about 1600 ℃ or at least 1800 ℃, and can be to be not more than approximately 2200 ℃ or be not more than approximately 2100 ℃.When moving heat source is away from crystal, the part of fusing becomes monocrystalline, and away from the fusing that becomes of the new regional area of seed crystal.This process continues the crystallization until the remainder of solid becomes always.In this process, solid can be oriented in to horizontal or vertical direction.Described specific growing method, such as melting area method (melting zone) and floating melting zone method (floating zone), belongs to the generally labeling that is called fusion area technology.Fusion area technology can be than crystal pulling method or bridgman growth method in conjunction with higher levels of doping agent, because the volatilization of material or decompose and can limit in crystal and will have the ability of how many doping agents.
Luminescent material can be the form of polycrystalline material.Can form such material by calcining, compacting, sintering or its arbitrary combination.In one embodiment, polycrystal powder (by hydrothermal method by precipitation in basic solution or by gas phase, obtain), described powder may be in the situation that using or not using tackiness agent compacting or thermic is close or assemble by sol-gel method.In another embodiment, compound can be monocrystalline or polycrystalline fibre (by micro-daraf(reciprocal of farad) (micro-pulling down) or obtain by EFG) or film (obtaining by CVD) or polycrystalline glass-ceramic.Luminescent material can be incorporated into can be in transparent material of main part, such as glass or plastics or liquid or crystal.Can carry out indirect excitation light-emitting material by the main consuming body material.
Subsequently, luminescent material reaction form substantially monocrystalline or polycrystalline material after, can make luminescent material annealing.In one embodiment, annealing temperature can be at least about 1100 ℃ or at least about 1200 ℃, and can be to be not more than approximately 1600 ℃ or be not more than approximately 1500 ℃.
In one embodiment, can in the environment of possibility that can help minimizing formation room, carry out the formation of luminescent material or optional annealing subsequently.In one embodiment, luminescent material is oxygenatedchemicals and can uses well-oxygenated environment.In another embodiment, luminescent material is halogen contained compound and can uses halogen-containing environment.In another embodiment, luminescent material is sulfocompound and can uses sulfur.
In the forming process of luminescent material or in annealing process subsequently, can use well-oxygenated environment.Well-oxygenated environment can comprise the material different from room weighting agent.Well-oxygenated environment can comprise O 2, O 3, NO, N 2o, CO 2or its arbitrary combination.On relative basis, in one embodiment, well-oxygenated environment comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the oxidizing substance different from room weighting agent of 20 volume %, and in another embodiment, well-oxygenated environment comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the oxidizing substance of approximately 40 volume %.For pressure, in another embodiment, well-oxygenated environment comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the oxidizing substance different from room weighting agent of 20kPa, and in another embodiment, well-oxygenated environment comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the oxidizing substance different from room weighting agent of about 40kPa.
In annealing process after luminescent material forms, can use halogen-containing environment.Halogen-containing environment can comprise the material different from room weighting agent.Halogen-containing environment can comprise NH 4cl, NH 4br, NH 4i, CBr 4, CCl 4, CI 4, CHBr 3, CHCl 3, CHI 3, CH 2br 2, CH 2cl 2, CH 2i 2or its arbitrary combination.On relative basis, in one embodiment, halogen-containing environment comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the halogen-containing material different from room weighting agent of 20 volume %, and in another embodiment, halogen-containing environment comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the halogen-containing material of approximately 40 volume %.For pressure, in another embodiment, halogen-containing environment comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the halogen-containing material different from room weighting agent of 20kPa, and in another embodiment, halogen-containing environment comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the halogen-containing material different from room weighting agent of about 40kPa.
In the forming process of luminescent material or in annealing process subsequently, can use sulfur.Sulfur can comprise the material different from room weighting agent.Sulfur comprises (NH 4) 2s, C 6h 4s, H 2s, S or its arbitrary combination.On relative basis, in one embodiment, sulfur comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the S-contained substance different from room weighting agent of 20 volume %, and in another embodiment, sulfur comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the S-contained substance of approximately 40 volume %.For pressure, in another embodiment, sulfur comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the S-contained substance different from room weighting agent of 20kPa, and in another embodiment, sulfur comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the S-contained substance different from room weighting agent of about 40kPa.
Can be further processed to form product.Such processing can comprise that cutting, polishing, grinding etc. are to form for the desired shape of application-specific.
Can form scintillator or useful other flicker devices in many devices with luminescent material.Fig. 1 illustrates an embodiment of device 100, and it comprises scintillator 122, photoconduction 124, optical sensor 126 and control unit 128.Scintillator 122 can comprise aforesaid luminescent material.Photoconduction 124 is substantial transparent for the twinkling light of being launched by scintillator 122.Optical sensor 126 can generate electronics in response to the twinkling light receiving from scintillator 122.Optical sensor 126 can be photomultiplier, photorectifier, avalanche diode etc.Scintillator 122, photoconduction 124 and optical sensor 126 can be coupled optically.Although it is that space separates that scintillator 122, photoconduction 124 and optical sensor 126 are shown as, photoconduction 124 can directly contact with scintillator 122 or optical sensor 126.In another embodiment, can scintillator 122, photoconduction 124 and optical sensor 126 be coupled with the silicon gel of coupling material such as substantial transparent.The inside that scintillator 122, photoconduction 124 and optical sensor 126 can be positioned at one or more housings makes surround lighting or other less desirable radiation can not arrive optical sensor 126.Control unit 128 is electrically coupled to optical sensor 126.In normal running, can pass through scintillator 122 trapped radiations, and scintillator 122 is in response to receiving target Radiation Emission twinkling light.By optical sensor 126, receive twinkling light, its generation is transmitted to the electronic signal of control unit 128.Control unit 128 comprises hardware, firmware or software, it is configured such that control unit 128 can generate the information about target radiation, type (x-ray such as radiation, gamma-radiation, beta-particle etc.), source or its arbitrary combination of yield of radiation, the captive position of radiation or radiation.
Device can be radiation detecting apparatus, such as medical imaging apparatus, well logging apparatus, safety inspection device etc.In a specific embodiment, can, by radiation detection system for gamma-rays analysis, such as single positron emission tomography (SPECT) or positron emission fault (PET), analyze.In another embodiment, can be by luminescent material for other application beyond radiation detection.For example, device can comprise particularly monochromatic luminescence emissions device, for UV spectrum, visible and IR, and as for Wavelength conversion system, Laser Devices for example.In such device, can be replaced being coupled to by lens or another suitable optics the control unit of scintillator 122 and photoconduction 124 and optical sensor 126.Can use another device of luminescent material can also comprise optical data storage device.
For many materials particularly semi-conductor, optical flare body, laser crystals and pottery, the use of room weighting agent can make it possible to omit annealing steps.Especially, the use at forming process Vacancy weighting agent can be so that single solution can compensate metastable phase (phase metastable) material as the room in lutetium aluminium uhligite (LuAP).
In addition, vacant weighting agent can comprise room filling atom and other atoms.Other atoms can be volatilized and are not incorporated in luminescent material.Alternatively, other atoms can be low-level and not be incorporated in the matrix of luminophor in luminescent material.
Further, room weighting agent makes room filling atom before sintering can be incorporated into melt or body, comprise the environmental facies ratio of the corresponding atom of negatively charged ion such as O, S and X (wherein X is halogen) with use, it is the more effective method in conjunction with such negatively charged ion.Therefore, in forming luminescent material, can use the environment of inert environments or less infringement device.
According to the described luminescent material of concept described herein, there is unusual good light output, energy resolution, linearity, fall time and persistence characteristic.Linearity refers to that scintillation crystal can reach perfect linear scaling how well between quantity of radiant energy and light output.Linear can being measured as from perfect linear departing from.The energy of radiation no matter, has the energy that photon/unit that perfect linear scintillation crystal will always produce equal amts absorbs.Therefore, it is zero from perfect linear departing from.In one embodiment, the twilight sunset that comprises the luminescent material of mixing cerium LYSO compound with respect to x-radiation exposure during measured intensity after 100ms, can be less than 200ppm.In a specific embodiment, the improvement with less twilight sunset can be accompanied by the fall time of minimizing and the light productive rate of increase.Having the divalence of elementary charge compensative material or the existence of tetravalence state rare earth element can be so that luminescent material can keep elementary charge balance, but still realizes the benefit with divalence or tetravalence state rare earth element.
In one embodiment, can detect by colour-change the existence in room.When all by the rayed of white substantially, by determine can its corresponding base mateiral compare according to the color distortion of the luminescent material of any embodiment described herein, can change by quantized color.As used herein, except forming under without room weighting agent, corresponding base mateiral has the composition substantially the same with luminescent material.For example, the luminescent material forming according to a specific embodiment described herein can comprise can use CeO 2, Lu 2o 3and SiO 2form mix the positive silicic acid lutetium of cerium and as the ZnO of room weighting agent, and its corresponding base mateiral is to use CeO 2, Lu 2o 3and SiO 2form, but do not add any ZnO.
Can use formed sample for colour-change evaluation, it has the coarse of polished surface, fracture, or has carried out another suitable sample preparation.Can guide white light to make it directed perpendicular to surface, at a certain angle rather than perpendicular to surface or from a plurality of light sources of the different angles orientation with respect to surperficial.Can determine colour-change with one or more different technologies.
In one embodiment, can use CIE1976 color space coordinate (L*, a* and b*).Can use the Cary6000i board spectrophotometer from Varian (being Agilent Technologies now, a part of Inc) to obtain CIE1976 color space coordinate.Luminescent material reflects the light of white substantially at color space coordinate L1*, a1*, the b1* of CIE1976 color space coordinate L*, a* corresponding to luminescent material and b*.Corresponding base mateiral is reflecting the light of white substantially corresponding to corresponding CIE1976 color space coordinate L*, the a* of base mateiral and the color space coordinate L2* of b*, a2*, b2*.Color distortion between luminescent material and basic compound can be to make | al*-a2*| is not more than approximately 9, and | bl*-b2*| is not more than approximately 9.In another embodiment, | a1*-a2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5 or be not more than approximately 0.2, be not more than approximately 0.09, be not more than approximately 0.05 or be not more than approximately 0.01, and | b1*-b2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5 or be not more than approximately 0.2, be not more than approximately 0.09, be not more than approximately 0.05 or be not more than approximately 0.01.In another embodiment, | L1*-L2*| is not more than approximately 9, is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5 or be not more than approximately 0.2.
As optional color space coordinate, can use catoptrical wavelength.Luminescent material reflects the light of white substantially at the first wavelength, and its corresponding basic compound reflects the light of white substantially in second wave length.In one embodiment, the first and second wavelength are to be not more than each other about 50nm apart, to be not more than about 30nm apart each other, to be not more than about 20nm, to be not more than about 15nm, to be not more than about 9nm, to be not more than about 5nm, to be not more than about 2nm.
In another embodiment, can use the special spectrum of wavelength.In an example, when the enough balances of elementary charge, luminescent material is colourless, and if elementary charge there is no enough balances, similarly scintillator compound has yellow color.Can compare scintillator compound and at 400nm, arrive the catoptrical intensity of 700nm wavelength.If data significant difference, can determine colour-change.Alternatively, can only use the irradiation luminous material of blue light (light for example, in wavelength is 400nm to 450nm scope with emission maximum).Compare with the luminescent material with yellow color, colourless luminescent material can reflect more blue light substantially.
In another example, when the enough balances of elementary charge, different luminescent materials has yellow color, and if elementary charge there is no enough balances, another kind of like the scintillator compound viridescent color of tool.Can compare scintillator compound and at 400nm, arrive the catoptrical intensity of 700nm wavelength.Can analyze with the light of different colours.For example, when only using the irradiation luminous material of green light (light, in wavelength is 500nm to 550nm scope with emission maximum), can obtain first group of data.For example, while only using the irradiation luminous material of red light (light, in wavelength is 650nm to 700nm scope with emission maximum), can obtain second group of data.Compare with the luminescent material with green color, yellow luminescent material can reflect more red light and green light still less substantially.
In addition, owing to comparing with the position of close sample or other body edges, near the center of sample or other bodies, there is less room, so room weighting agent can help to be created in the luminescent material in whole sample or other bodies with more uniform functional performance.Sample or other bodies can be cut into less sample.For example, the sample of 10 * 2 * 2mm can be cut into the sample of ten 1 * 2 * 2.After preliminary UV or x-ray irradiation, can characterize less sample by known thermoluminescence analytical technology.At two-dimensional space, analyze: the light emission of sample (LE)/temperature (T).When starting slowly to heat up from low temperature, sample Department of Radiation light splitting under specific temperature levels, mean defect can de-catching.Final curve LE (T) generally includes the several peaks corresponding to the different heights of differing temps.These curves form sample in luminescent material and characterize (" feature ") with respect to the density of defect and the uniqueness of energy level.Specific test or test condition should be identical for all samples.Compared with the LE of small sample (T) curve, it can be the function of the position in primary sample or body.Compare with the corresponding base mateiral of luminescent material, the luminescent material forming according to any method described herein will have Thermo-luminescence LE (T) shape being obtained compared with small sample by difference approaching very much.
Many different aspects and embodiment are possible.This paper describes some in those aspects and embodiment.After reading this specification sheets, it will be apparent to one skilled in the art that those aspects and embodiment are only illustrative and not limit the scope of the invention.In addition, it will be understood by those of skill in the art that, comprise that some embodiments of mimic channel can be implemented similarly by digital circuit, and vice versa.
Embodiment can according in following listed item any one or multinomial.
1. 1 kinds of methods of item, comprising:
Form following mixture:
Component corresponding to luminescent material; With
The room weighting agent that comprises room filling atom; And
From described mixture, form described luminescent material, wherein said luminescent material comprises that at least some are from the described room filling atom of described room weighting agent.
2. 1 kinds of methods of item, comprising:
Fusing corresponding to the component of luminescent material to form melt;
Room weighting agent is added in described melt; And
From luminescent material described in described melt composition, wherein said luminescent material comprises that at least some are from the described room filling atom of described room weighting agent.
Item 3. is according to the method described in item 1 or 2, wherein said room weighting agent also comprises other atoms, described other atoms comprise from described room fills the different element of the element of atom, and forms described luminescent material and make there is no that described other atoms from described room weighting agent are incorporated in the matrix of described luminescent material.
Item 4., according to the method described in item 3, is wherein incorporated into the degree in described luminescent material at any other atom from described room weighting agent, and described any other atom is substantially only combined in interstitial site.
Item 5. is according to the method described in item 1 or 2, wherein said room weighting agent also comprises other atoms, described other atoms comprise from described room fills the different element of the element of atom, and forms described luminescent material and make there is no that described other atoms from described room weighting agent are incorporated in described luminescent material.
Item 6. is according to the method described in any one in item 3 to 5, and wherein said other atoms comprise atoms metal.
Item 7. is according to the method described in any one in item 6, and wherein said atoms metal comprises Ba, Sn, Zn, Zr, Hf, Cd, Pb or its arbitrary combination.
Item 8. is according to the method described in any one in aforementioned, and it is O, S or X that atom is filled in wherein said room, and wherein X is halogen.
Item 9. is according to the method described in any one in aforementioned, and wherein said room weighting agent comprises BaO 2, SnO 2, ZnO or its arbitrary combination.
Item 10. is according to the method described in any one in aforementioned, wherein:
It is O that atom is filled in described room; And
In well-oxygenated environment, form described luminescent material.
11. according to the method described in any one in item 1 to 8, is also included in the described luminescent material of annealing in well-oxygenated environment.
Item 12. is according to the method described in item 10 or 11, and wherein said well-oxygenated environment comprises O 2, O 3, NO, N 20, CO 2or its arbitrary combination.
13. according to the method described in any one in item 10 to 12, and wherein said well-oxygenated environment comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the oxidizing substance different from described room weighting agent of 20 volume %.
14. according to the method described in any one in item 10 to 13, and wherein said well-oxygenated environment comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the oxidizing substance of approximately 40 volume %.
15. according to the method described in any one in item 10 to 14, and wherein said well-oxygenated environment comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the oxidizing substance different from described room weighting agent of 20kPa.
16. according to the method described in any one in item 10 to 15, and wherein said well-oxygenated environment comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the oxidizing substance different from described room weighting agent of about 40kPa.
Item 17. is according to the method described in any one in item 1 to 8, and wherein said room weighting agent comprises ZnX 2, ZrX 4, HfX 4, SnX 2or its arbitrary combination, wherein X is halogen.
Item 18. is according to the method described in any one in item 1 to 8 and 17, wherein:
It is X that atom is filled in described room; And
Described method is also included in the described luminescent material of annealing in halogen-containing environment.
Item 19. is according to the method described in item 18, and wherein said halogen-containing environment comprises NH 4cl, NH 4br, NH 4i, CBr 4, CCl 4, CI 4, CHBr 3, CHCl 3, CHI 3, CH 2br 2, CH 2cl 2, CH 2i 2or its arbitrary combination.
20. according to the method described in item 18 or 19, and wherein said halogen-containing environment comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the halogen-containing material different from described room weighting agent of 20 volume %.
21. according to the method described in any one in item 18 to 20, and wherein said halogen-containing environment comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the halogen-containing material different from described room weighting agent of approximately 40 volume %.
22. according to the method described in any one in item 18 to 21, and wherein said halogen-containing environment comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the halogen-containing material different from described room weighting agent of 20kPa.
23. according to the method described in any one in item 18 to 22, and wherein said halogen-containing environment comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the halogen-containing material different from described room weighting agent of about 40kPa.
Item 24. is according to the method described in any one in item 1 to 8, and wherein said room weighting agent comprises CdS, PbS 2, S or its arbitrary combination.
Item 25. is according to the method described in any one in item 1 to 8 and 24, wherein:
It is S that atom is filled in described room; And
In sulfur, form described luminescent material.
26. according to the method described in any one in item 1 to 8 and 24, is also included in the described luminescent material of annealing in sulfur.
Item 27. is according to the method described in item 24 or 25, and wherein said sulfur comprises (NH 4) 2s, C 6h 4s, H 2s, S or its arbitrary combination.
28. according to the method described in any one in item 25 to 27, and wherein said sulfur comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the S-contained substance different from described room weighting agent of 20 volume %.
29. according to the method described in any one in item 25 to 28, and wherein said sulfur comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the S-contained substance different from described room weighting agent of approximately 40 volume %.
30. according to the method described in any one in item 25 to 29, and wherein said sulfur comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the S-contained substance different from described room weighting agent of 20kPa.
31. according to the method described in any one in item 25 to 30, and wherein said sulfur comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the S-contained substance different from described room weighting agent of about 40kPa.
32. according to the method described in any one in aforementioned, wherein said room weighting agent be form described luminescent material parent material total mass at least about 0.0002 % by weight, at least about 0.001 % by weight, at least about 0.002 % by weight, at least about 0.02 % by weight, at least about 0.05 % by weight, at least about 0.11 % by weight or at least about 0.3 % by weight.
33. according to the method described in any one in aforementioned, and wherein said room weighting agent is being not more than approximately 50 % by weight, being not more than approximately 20 % by weight, being not more than approximately 9 % by weight, being not more than approximately 5 % by weight, being not more than approximately 2 % by weight, being not more than approximately 0.7 % by weight, being not more than approximately 0.2 % by weight, being not more than approximately 0.09 % by weight, being not more than approximately 0.02 % by weight or being not more than 0.01 % by weight of total mass that forms the parent material of described luminescent material.
34. according to the method described in any one in aforementioned, and the vaporization temperature of wherein said room weighting agent is in approximately 250 ℃ of the temperature of fusion of described luminescent material.
Item 35. is according to the method described in any one in aforementioned, and wherein said room weighting agent has the vaporization temperature higher than the temperature of fusion of described luminescent material.
36. according to the method described in item 35, the vaporization temperature of wherein said room weighting agent than the temperature of fusion of described luminescent material high at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.
37. according to the method described in item 35 or 36, wherein heats described mixture and is included in and forms the vaporization temperature that described mixture is heated to before described luminescent material at least described room weighting agent.
38. according to the method described in item 37, the vaporization temperature that wherein described mixture is heated to at least described room weighting agent carry out at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.
Item 39., according to the method described in item 37 or 38, also comprises:
Described mixture is cooled to approach to another temperature of the temperature of fusion of described luminescent material; And
By described mixture remain on described other temperature at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.
Item 40. is according to the method described in any one in item 1 to 34, and wherein said room weighting agent has the vaporization temperature lower than the temperature of fusion of described luminescent material.
41. according to the method described in item 40, the vaporization temperature of wherein said room weighting agent than the temperature of fusion of described luminescent material low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.
Item 42., according to the method described in any one in item 1 to 33, wherein forms described luminescent material from described mixture and comprises:
From described mixture, form body; And
Body described in sintering in sintering temperature and under higher than atmospheric sintering pressure.
43. according to the method described in item 42, and wherein described in sintering, body forms the ceramic body of described luminescent material.
44. according to the method described in item 42 or 44, and wherein said room weighting agent is not more than approximately 250 ℃ in normal atmosphere to the vaporization temperature under the pressure in the scope of described sintering pressure than described sintering temperature is low.
45. according to the method described in any one in item 42 to 44, wherein said room weighting agent normal atmosphere to the described vaporization temperature under the pressure in the scope of described sintering pressure than described sintering temperature low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.
Item 46., according to the method described in any one in item 42 to 45, also comprises:
Described body is heated under the first pressure to the first temperature, wherein said the first temperature is vaporization temperature described in the pact of described room weighting agent under described the first pressure;
By described body be maintained at about at described the first temperature at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes; And
Described body is heated to the described sintering temperature higher than described the first temperature.
Item 47. is according to the method described in any one in aforementioned, wherein compare with the corresponding base mateiral of the substantially the same size of described luminescent material, the body of described luminescent material has more uniform thermoluminescence Characteristics in whole described body, and the size of wherein said body is 2mm at least.
Item 48. is according to the method described in any one in aforementioned, and wherein said luminescent material is with respect to intensity measured during x-ray irradiation, after 20ms, to have the scintillation material of the twilight sunset that is less than 200ppm.
Item 49. is according to the method described in any one in aforementioned, wherein said luminescent material, wherein compare with the corresponding base mateiral of described luminescent material, described luminescent material is the energy resolution with the output of larger light, less value, lower twilight sunset, shorter fall time, the scintillation material of more proportional response or its arbitrary combination within the scope of certain irradiation energy.
50. 1 kinds of luminescent materials, wherein compare with the corresponding base mateiral of the substantially the same size of described luminescent material, and the body of described luminescent material has more uniform thermoluminescence Characteristics in whole described body, and the size of wherein said body is 2mm at least.
51. 1 kinds of luminescent materials, comprise compare to the corresponding base mateiral of described luminescent material there is the energy resolution of larger light output, less value, lower twilight sunset, shorter fall time, the scintillation material of more proportional response or its arbitrary combination within the scope of certain irradiation energy.
Item 52., according to method or luminescent material described in any one in aforementioned, is wherein compared with described corresponding base mateiral, and described luminescent material has larger light output.
Item 53., according to method or luminescent material described in any one in aforementioned, is wherein compared with described corresponding base mateiral, and described luminescent material is the scintillation material with the energy resolution of less value.
Item 54., according to method or luminescent material described in any one in aforementioned, is wherein compared with described corresponding base mateiral, and described luminescent material has lower twilight sunset.
Item 55., according to method or luminescent material described in any one in aforementioned, is wherein compared with described corresponding base mateiral, and described luminescent material is the scintillation material with shorter fall time.
Item 56., according to method or luminescent material described in any one in aforementioned, is wherein compared with described corresponding base mateiral, and described luminescent material is within the scope of certain irradiation energy, to have the scintillation material of more proportional response.
57. according to method or luminescent material described in any one in aforementioned, the twilight sunset of wherein said luminescent material with respect to x-ray irradiation during measured described intensity after 20ms, be less than 200ppm.
Item 58. is according to method or luminescent material described in any one in aforementioned, wherein:
Described luminescent material can reflect the light of white substantially at color space coordinate L1*, a1*, the b1* of CIE1976 color space coordinate L*, a* corresponding to described luminescent material and b*;
The corresponding base mateiral of described luminescent material can reflect the light of white substantially at color space coordinate L2*, a2*, the b2* of CIE1976 color space coordinate L*, a* corresponding to described corresponding base mateiral and b*;
| a1*-a2*| is not more than approximately 9; And
| b1*-b2*| is not more than approximately 9.
Item 59. is according to method or luminescent material described in item 58, wherein:
| a1*-a2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5, is not more than approximately 0.2, is not more than approximately 0.09, is not more than approximately 0.05 or be not more than approximately 0.01; And
| b1*-b2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5 or be not more than approximately 0.2, be not more than approximately 0.09, be not more than approximately 0.05 or be not more than approximately 0.01.
Item 60. is according to the method described in item 58 or 59 or luminescent material, wherein | and L1*-L2*| is not more than approximately 9.
61. according to method or luminescent material described in item 60, wherein | and L1*-L2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5 or be not more than approximately 0.2.
Item 62. is according to method or luminescent material described in any one in aforementioned, wherein:
Described luminescent material can reflect the light of white substantially at the first wavelength;
The corresponding base mateiral of described luminescent material can reflect the light of white substantially in second wave length; And
Described the first wavelength and second wave length are to be not more than each other about 50nm apart.
63. according to method or luminescent material described in item 62, and wherein said the first wavelength and second wave length are to be not more than each other about 30nm apart, to be not more than about 20nm, to be not more than about 15nm, to be not more than about 9nm, to be not more than about 5nm, to be not more than about 2nm.
Item 64. is according to method or luminescent material described in any one in item 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-silicon-oxygen compound.
Item 65. is according to method or luminescent material described in any one in item 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-boron-nitrogen compound.
Item 66. is according to method or luminescent material described in any one in item 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-aluminium-oxygen compound, and wherein said metal is different from aluminium, and described metal-aluminium-oxygen compound does not comprise the silicon of significant quantity.
Item 67. is according to method or luminescent material described in any one in item 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-phosphorus-oxygen compound.
Item 68. is according to method or luminescent material described in any one in item 1 to 8 and 24 to 63, and wherein said luminescent material comprises metal sulphide compound.
Item 69. is according to method or luminescent material described in any one in item 1 to 16 and 24 to 63, and wherein said luminescent material comprises metal-oxygen-sulphur compound.
Item 70. is according to method or luminescent material described in any one in item 1 to 8,15 to 23 and 32 to 63, and wherein said luminescent material comprises metal halide.
Item 71. is according to method or luminescent material described in any one in item 1 to 23 and 32 to 63, and wherein said luminescent material comprises metal-oxygen-halogen compounds.
72. according to method or luminescent material described in any one in aforementioned, and wherein said luminescent material is monocrystalline substantially.
Item 73. is according to method or luminescent material described in any one in item 1 to 71, and wherein said luminescent material is polycrystalline material.
Item 74. is according to method or luminescent material described in any one in aforementioned, and wherein said luminescent material comprises rare earth element.
Item 75. is according to method or luminescent material described in item 74, and wherein said rare earth element is the main ingredient of described luminescent material.
76. 1 kinds of radiation detecting apparatus of item, comprising:
Scintillator, comprises described luminescent material by preparing according to the method described in any one in aforementioned or according to the luminescent material described in any one in aforementioned; With
Optical sensor, is configured to receive the twinkling light from described scintillator.
Item 77. is according to the radiation detecting apparatus described in item 76, and wherein said radiation detecting apparatus comprises medical imaging apparatus, well logging apparatus or safety inspection device.
78. 1 kinds of positron emission computerized tomography devices, comprise described luminescent material by preparing according to the method described in any one in item 1 to 75 or according to the luminescent material described in any one in item 1 to 75.
79. 1 kinds of Laser Devices, comprise described luminescent material by preparing according to the method described in any one in item 1 to 75 or according to the luminescent material described in any one in item 1 to 75.
80. 1 kinds of optical data storage devices, comprise described luminescent material by preparing according to the method described in any one in item 1 to 75 or according to the luminescent material described in any one in item 1 to 75.
embodiment
Concept disclosed herein will further describe in an embodiment, and described embodiment does not limit the invention scope of describing in claim.Embodiment shows the performance of the scintillation crystal of different compositions.For object easily, in this embodiment part disclosed numerical value can be similar to or round up.
embodiment 1
Embodiment 1 relates to oxide compound, particularly LYSO:Ce material.When forming LYSO:Ce scintillation material by SnO 2or ZnO is added into component and at twinkling light output facet, produces the result of improving.By SnO 2or ZnO compound is added directly to melt together with forming the stoichiometric mixture of oxide compound of LYSO:Ce phase.Table 1 comprises the table of LYSO material; " ref " refers to and wherein do not add SnO 2or the reference of ZnO.During residue is bathed accordingly afterwards, the glow discharge spectrometry of application (GDMS) analysis not have to find the Sn of (lower than 0.1ppm) remnants or any vestige of Zn in the listed all samples of table 1 growing crystal or in growth.For 10 * 10 * 10mm 3lYSO sample applied core and characterized.
Table 1
When using room weighting agent, the data presentation in table 1 goes out beyond thought higher light output.Compare with their corresponding basic compounds separately, for the sample with Ca co-dopant, room weighting agent has improved approximately 29% light output, and for the sample with Mg co-dopant, room weighting agent has improved approximately 22% light output.
The twilight sunset of test sample.By determining that the light output from sample characterizes, it is to detect with near wavelength visible spectrum 550nm by silicon photomultiplier (SiPM).At 20ms and 500ms, collect data.Data are listed in table 2.
Table 2
When using room weighting agent, the data presentation in table 2 goes out beyond thought less twilight sunset.Compare with their corresponding basic compounds separately, for the sample with Ca co-dopant, room weighting agent has reduced approximately 50% twilight sunset.
Prepare other sample, the amount of its Vacancy weighting agent.When the ZnO of 0.1 % by weight or SnO (total mass based on load) are added into melt, improve not remarkable.ZnO or SnO in 0.5 % by weight 2time, realized beyond thought result, such as those in table 1 and table 2.In 1.0 % by weight or 2.0 % by weight, it is saturated that result becomes, and demonstrates and remarkable improvement in the substantially the same characteristic of 0.5 % by weight and flicker free parameter.
embodiment 2
Embodiment 2 relates to halogenide, particularly LaBr 3: Ce material.When forming LaBr 3: during Ce scintillation material by ZnBr 2, ZrBr 4or HfBR 4be added into component and at twinkling light output facet, produce the result of improving.By ZnBr 2, ZrBr 4or HfBR 4compound is added directly to melt together with halid stoichiometric mixture.There is not (lower than 0.1ppm) as Zn, Sn, Zr or Hf in GDMS Analysis deterrmination cation impurity in crystal.
Table 3
At growth phase, for the original position in Br room, eliminate and demonstrate for LaBr 3: the improvement of Ce detector light productive rate.With oxide compound scintillator compounds seemingly, halide scintillator has the flicker parameter of the certain concentration of being improved to, and higher than this concentration, does not observe further significantly and improves.Yet, for LaBr 3, it is much lower that the usage quantity of room weighting agent can be compared LYSO.Concentration in the scope of 0.001 % by weight to 0.01 % by weight (total mass based on load) demonstrates the lasting improvement as the material electronics performance of the function of room weighting agent concentration.In 0.01 % by weight, starting Electronic Performance becomes saturated and does not observe material flicker (luminous) characteristic of further significantly improving.
It should be noted that and do not require above all these activities that illustrate in generality explanation or these embodiment, can not require a part of a specific activities, and can carry out one or more other activities except described those.Still further, the order of these activities being listed must not be the order of carrying out them.
For the sake of clarity under the background of the embodiment of a plurality of separation, some feature described here also can be combined and provide in a single embodiment.In contrast, for simplicity, a plurality of different characteristicss of describing in the background of a single embodiment can also be respectively or are provided in the mode of any sub-portfolio.In addition, the mentioned numerical value illustrating with scope is included in each value within this scope.
For a plurality of specific embodiments, multiple benefit, other advantage and the solution of problem have been described above.Yet the solution of these benefits, advantage, problem and any one or multinomial feature (they can cause any benefit, advantage or solution occur or become more outstanding) must not be construed as critical, a desired or requisite feature of any or all claim.
The explanation of these embodiments described here and displaying aim to provide the general understanding of the structure of different embodiments.These explanations and displaying are not intended to as a comprehensive and comprehensive description using these structures described here or the device of method and all elements of system and feature.Embodiment separately also can be provided by the combination of a single embodiment, and in contrast, for simplicity, a plurality of different characteristicss of describing in the background of a single embodiment can also be respectively or are provided in the mode of any sub-portfolio.In addition, the mentioned numerical value illustrating with scope is included in each value within this scope.For those skilled in the art, only after reading this specification sheets, can know many other embodiments.Other embodiments can be used and be derivative from the disclosure, can carry out a structure replacement, logic replacement or another kind of change like this without deviating from the scope of the present disclosure.Therefore, present disclosure should be considered to illustrative and not restrictive.

Claims (80)

1. a method, comprising:
Form following mixture:
Component corresponding to luminescent material; With
The room weighting agent that comprises room filling atom; And
From described mixture, form described luminescent material, wherein said luminescent material comprises that at least some are from the described room filling atom of described room weighting agent.
2. a method, comprising:
Fusing corresponding to the component of luminescent material to form melt;
Room weighting agent is added in described melt; And
From luminescent material described in described melt composition, wherein said luminescent material comprises that at least some are from the described room filling atom of described room weighting agent.
3. method according to claim 1 and 2, wherein said room weighting agent also comprises other atoms, described other atoms comprise from described room fills the different element of the element of atom, and forms described luminescent material and make there is no that described other atoms from described room weighting agent are incorporated in the matrix of described luminescent material.
4. method according to claim 3, is wherein incorporated into the degree in described luminescent material at any other atom from described room weighting agent, and described any other atom is substantially only combined in interstitial site.
5. method according to claim 1 and 2, wherein said room weighting agent also comprises other atoms, described other atoms comprise from described room fills the different element of the element of atom, and forms described luminescent material and make there is no that described other atoms from described room weighting agent are incorporated in described luminescent material.
6. according to the method described in any one in claim 3 to 5, wherein said other atoms comprise atoms metal.
7. according to the method described in any one in claim 6, wherein said atoms metal comprises Ba, Sn, Zn, Zr, Hf, Cd, Pb or its arbitrary combination.
8. according to method in any one of the preceding claims wherein, it is O, S or X that atom is filled in wherein said room, and wherein X is halogen.
9. according to method in any one of the preceding claims wherein, wherein said room weighting agent comprises BaO 2, SnO 2, ZnO or its arbitrary combination.
10. according to method in any one of the preceding claims wherein, wherein:
It is O that atom is filled in described room; And
In well-oxygenated environment, form described luminescent material.
11. according to the method described in any one in claim 1 to 8, is also included in the described luminescent material of annealing in well-oxygenated environment.
12. according to the method described in claim 10 or 11, and wherein said well-oxygenated environment comprises O 2, O 3, NO, N 2o, CO 2or its arbitrary combination.
13. according to claim 10 to the method described in any one in 12, and wherein said well-oxygenated environment comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the oxidizing substance different from described room weighting agent of 20 volume %.
14. according to claim 10 to the method described in any one in 13, and wherein said well-oxygenated environment comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the oxidizing substance of approximately 40 volume %.
15. according to claim 10 to the method described in any one in 14, and wherein said well-oxygenated environment comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the oxidizing substance different from described room weighting agent of 20kPa.
16. according to claim 10 to the method described in any one in 15, and wherein said well-oxygenated environment comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the oxidizing substance different from described room weighting agent of about 40kPa.
17. according to the method described in any one in claim 1 to 8, and wherein said room weighting agent comprises ZnX 2, ZrX 4, HfX 4, SnX 2or its arbitrary combination, wherein X is halogen.
18. according to the method described in any one in claim 1 to 8 and 17, wherein:
It is X that atom is filled in described room; And
Described method is also included in the described luminescent material of annealing in halogen-containing environment.
19. methods according to claim 18, wherein said halogen-containing environment comprises NH 4cl, NH 4br, NH 4i, CBr 4, CCl 4, CI 4, CHBr 3, CHCl 3, CHI 3, CH 2br 2, CH 2cl 2, CH 2i 2or its arbitrary combination.
20. according to the method described in claim 18 or 19, and wherein said halogen-containing environment comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the halogen-containing material different from described room weighting agent of 20 volume %.
21. according to claim 18 to the method described in any one in 20, and wherein said halogen-containing environment comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the halogen-containing material different from described room weighting agent of approximately 40 volume %.
22. according to claim 18 to the method described in any one in 21, and wherein said halogen-containing environment comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the halogen-containing material different from described room weighting agent of 20kPa.
23. according to claim 18 to the method described in any one in 22, and wherein said halogen-containing environment comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the halogen-containing material different from described room weighting agent of about 40kPa.
24. according to the method described in any one in claim 1 to 8, and wherein said room weighting agent comprises CdS, PbS 2, S or its arbitrary combination.
25. according to the method described in any one in claim 1 to 8 and 24, wherein:
It is S that atom is filled in described room; And
In sulfur, form described luminescent material.
26. according to the method described in any one in claim 1 to 8 and 24, is also included in the described luminescent material of annealing in sulfur.
27. according to the method described in claim 24 or 25, and wherein said sulfur comprises (NH 4) 2s, C 6h 4s, H 2s, S or its arbitrary combination.
28. according to the method described in any one in claim 25 to 27, and wherein said sulfur comprises at least about 1.4 volume %, at least about 5 volume %, at least about 11 volume %, at least about 15 volume % or at least about the S-contained substance different from described room weighting agent of 20 volume %.
29. according to the method described in any one in claim 25 to 28, and wherein said sulfur comprises and is not more than 100 volume %, is not more than approximately 90 volume %, is not more than approximately 75 volume %, is not more than approximately 50 volume % or is not more than the S-contained substance different from described room weighting agent of approximately 40 volume %.
30. according to the method described in any one in claim 25 to 29, and wherein said sulfur comprises at least about 1.4kPa, at least about 5kPa, at least about 11kPa, at least about 15kPa or at least about the S-contained substance different from described room weighting agent of 20kPa.
31. according to the method described in any one in claim 25 to 30, and wherein said sulfur comprises and is not more than 101kPa, is not more than about 90kPa, is not more than about 75kPa, is not more than about 50kPa or is not more than the S-contained substance different from described room weighting agent of about 40kPa.
32. according to method in any one of the preceding claims wherein, wherein said room weighting agent be form described luminescent material parent material total mass at least about 0.0002 % by weight, at least about 0.001 % by weight, at least about 0.002 % by weight, at least about 0.02 % by weight, at least about 0.05 % by weight, at least about 0.11 % by weight or at least about 0.3 % by weight.
33. according to method in any one of the preceding claims wherein, and wherein said room weighting agent is being not more than approximately 50 % by weight, being not more than approximately 20 % by weight, being not more than approximately 9 % by weight, being not more than approximately 5 % by weight, being not more than approximately 2 % by weight, being not more than approximately 0.7 % by weight, being not more than approximately 0.2 % by weight, being not more than approximately 0.09 % by weight, being not more than approximately 0.02 % by weight or being not more than 0.01 % by weight of total mass that forms the parent material of described luminescent material.
34. according to method in any one of the preceding claims wherein, and the vaporization temperature of wherein said room weighting agent is in approximately 250 ℃ of the temperature of fusion of described luminescent material.
35. according to method in any one of the preceding claims wherein, and wherein said room weighting agent has the vaporization temperature higher than the temperature of fusion of described luminescent material.
36. methods according to claim 35, the vaporization temperature of wherein said room weighting agent than the temperature of fusion of described luminescent material high at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.
37. according to the method described in claim 35 or 36, wherein heats described mixture and is included in and forms the vaporization temperature that described mixture is heated to before described luminescent material at least described room weighting agent.
38. according to the method described in claim 37, the vaporization temperature that wherein described mixture is heated to at least described room weighting agent carry out at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.
39. according to the method described in claim 37 or 38, also comprises:
Described mixture is cooled to approach to another temperature of the temperature of fusion of described luminescent material; And
By described mixture remain on described other temperature at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes.
40. according to the method described in any one in claims 1 to 34, and wherein said room weighting agent has the vaporization temperature lower than the temperature of fusion of described luminescent material.
41. according to the method described in claim 40, the vaporization temperature of wherein said room weighting agent than the temperature of fusion of described luminescent material low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.
42. according to the method described in any one in claims 1 to 33, wherein from described mixture, forms described luminescent material and comprises:
From described mixture, form body; And
Body described in sintering in sintering temperature and under higher than atmospheric sintering pressure.
43. according to the method described in claim 42, and wherein described in sintering, body forms the ceramic body of described luminescent material.
44. according to the method described in claim 42 or 44, and wherein said room weighting agent is not more than approximately 250 ℃ in normal atmosphere to the vaporization temperature under the pressure in the scope of described sintering pressure than described sintering temperature is low.
45. according to the method described in any one in claim 42 to 44, wherein said room weighting agent normal atmosphere to the described vaporization temperature under the pressure in the scope of described sintering pressure than described sintering temperature low at least about 5 ℃, at least about 11 ℃, at least about 20 ℃, at least about 50 ℃ or at least 105 ℃.
46. according to the method described in any one in claim 42 to 45, also comprises:
Described body is heated under the first pressure to the first temperature, wherein said the first temperature is vaporization temperature described in the pact of described room weighting agent under described the first pressure;
By described body be maintained at about at described the first temperature at least about 1.1 minutes, at least about 5 minutes, at least about 11 minutes, at least about 15 minutes or at least about time period of 20 minutes; And
Described body is heated to the described sintering temperature higher than described the first temperature.
47. according to method in any one of the preceding claims wherein, wherein compare with the corresponding base mateiral of the substantially the same size of described luminescent material, the body of described luminescent material has more uniform thermoluminescence Characteristics in whole described body, and the size of wherein said body is 2mm at least.
48. according to method in any one of the preceding claims wherein, and wherein said luminescent material is with respect to intensity measured during x-ray irradiation, after 20ms, to have the scintillation material of the twilight sunset that is less than 200ppm.
49. according to method in any one of the preceding claims wherein, wherein said luminescent material, wherein compare with the corresponding base mateiral of described luminescent material, described luminescent material is the energy resolution with the output of larger light, less value, lower twilight sunset, shorter fall time, the scintillation material of more proportional response or its arbitrary combination within the scope of certain irradiation energy.
50. 1 kinds of luminescent materials, wherein compare with the corresponding base mateiral of the substantially the same size of described luminescent material, and the body of described luminescent material has more uniform thermoluminescence Characteristics in whole described body, and the size of wherein said body is 2mm at least.
51. 1 kinds of luminescent materials, comprise compare to the corresponding base mateiral of described luminescent material there is the energy resolution of the output of larger light, less value, lower twilight sunset, shorter fall time, the scintillation material of more proportional response or its arbitrary combination within the scope of certain irradiation energy.
52. according to method in any one of the preceding claims wherein or luminescent material, wherein compares with described corresponding base mateiral, and described luminescent material has larger light output.
53. according to method in any one of the preceding claims wherein or luminescent material, wherein compares with described corresponding base mateiral, and described luminescent material is the scintillation material with the energy resolution of less value.
54. according to method in any one of the preceding claims wherein or luminescent material, wherein compares with described corresponding base mateiral, and described luminescent material has lower twilight sunset.
55. according to method in any one of the preceding claims wherein or luminescent material, wherein compares with described corresponding base mateiral, and described luminescent material is the scintillation material with shorter fall time.
56. according to method in any one of the preceding claims wherein or luminescent material, wherein compares with described corresponding base mateiral, and described luminescent material is within the scope of certain irradiation energy, to have the scintillation material of more proportional response.
57. according to method in any one of the preceding claims wherein or luminescent material, the twilight sunset of wherein said luminescent material with respect to x-ray irradiation during measured described intensity after 20ms, be less than 200ppm.
58. according to method in any one of the preceding claims wherein or luminescent material, wherein:
Described luminescent material can reflect the light of white substantially at color space coordinate L1*, a1*, the b1* of CIE1976 color space coordinate L*, a* corresponding to described luminescent material and b*;
The corresponding base mateiral of described luminescent material can reflect the light of white substantially at color space coordinate L2*, a2*, the b2* of CIE1976 color space coordinate L*, a* corresponding to described corresponding base mateiral and b*;
| a1*-a2*| is not more than approximately 9; And
| b1*-b2*| is not more than approximately 9.
59. according to the method described in claim 58 or luminescent material, wherein:
| a1*-a2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5, is not more than approximately 0.2, is not more than approximately 0.09, is not more than approximately 0.05 or be not more than approximately 0.01; And
| b1*-b2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5 or be not more than approximately 0.2, be not more than approximately 0.09, be not more than approximately 0.05 or be not more than approximately 0.01.
60. according to the method described in claim 58 or 59 or luminescent material, wherein | and L1*-L2*| is not more than approximately 9.
61. according to the method described in claim 60 or luminescent material, wherein | and L1*-L2*| is not more than approximately 5, is not more than approximately 3, is not more than approximately 2, is not more than approximately 1.5, is not more than approximately 0.9, is not more than approximately 0.5 or be not more than approximately 0.2.
62. according to method in any one of the preceding claims wherein or luminescent material, wherein:
Described luminescent material can reflect the light of white substantially at the first wavelength;
The corresponding base mateiral of described luminescent material can reflect the light of white substantially in second wave length; And
Described the first wavelength and second wave length are to be not more than each other about 50nm apart.
63. according to the method described in claim 62 or luminescent material, and wherein said the first wavelength and second wave length are to be not more than each other about 30nm apart, to be not more than about 20nm, to be not more than about 15nm, to be not more than about 9nm, to be not more than about 5nm, to be not more than about 2nm.
64. according to method or luminescent material described in any one in claim 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-silicon-oxygen compound.
65. according to method or luminescent material described in any one in claim 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-boron-nitrogen compound.
66. according to method or luminescent material described in any one in claim 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-aluminium-oxygen compound, and wherein said metal is different from aluminium, and described metal-aluminium-oxygen compound does not comprise the silicon of significant quantity.
67. according to method or luminescent material described in any one in claim 1 to 16 and 32 to 63, and wherein said luminescent material comprises metal-phosphorus-oxygen compound.
68. according to method or luminescent material described in any one in claim 1 to 8 and 24 to 63, and wherein said luminescent material comprises metal sulphide compound.
69. according to method or luminescent material described in any one in claim 1 to 16 and 24 to 63, and wherein said luminescent material comprises metal-oxygen-sulphur compound.
70. according to method or luminescent material described in any one in claim 1 to 8,15 to 23 and 32 to 63, and wherein said luminescent material comprises metal halide.
71. according to method or luminescent material described in any one in claim 1 to 23 and 32 to 63, and wherein said luminescent material comprises metal-oxygen-halogen compounds.
72. according to method in any one of the preceding claims wherein or luminescent material, and wherein said luminescent material is monocrystalline substantially.
73. according to the method described in any one in claim 1 to 71 or luminescent material, and wherein said luminescent material is polycrystalline material.
74. according to method in any one of the preceding claims wherein or luminescent material, and wherein said luminescent material comprises rare earth element.
75. according to the method described in claim 74 or luminescent material, and wherein said rare earth element is the main ingredient of described luminescent material.
76. 1 kinds of radiation detecting apparatus, comprising:
Scintillator, comprises described luminescent material by preparing according to method in any one of the preceding claims wherein or according to luminescent material in any one of the preceding claims wherein; With
Optical sensor, is configured to receive the twinkling light from described scintillator.
77. according to the radiation detecting apparatus described in claim 76, and wherein said radiation detecting apparatus comprises medical imaging apparatus, well logging apparatus or safety inspection device.
78. 1 kinds of positron emission computerized tomography devices, comprise described luminescent material by preparing according to the method described in any one in claim 1 to 75 or according to the luminescent material described in any one in claim 1 to 75.
79. 1 kinds of Laser Devices, comprise described luminescent material by preparing according to the method described in any one in claim 1 to 75 or according to the luminescent material described in any one in claim 1 to 75.
80. 1 kinds of optical data storage devices, comprise described luminescent material by preparing according to the method described in any one in claim 1 to 75 or according to the luminescent material described in any one in claim 1 to 75.
CN201280055332.9A 2011-11-24 2012-11-23 luminescent material and forming method thereof Active CN103930518B (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
FR1160738 2011-11-24
FR1160738 2011-11-24
US201261584490P 2012-01-09 2012-01-09
US61/584490 2012-01-09
US61/584,490 2012-01-09
PCT/US2012/066459 WO2013078460A1 (en) 2011-11-24 2012-11-23 Luminescent material and a process of forming the same

Publications (2)

Publication Number Publication Date
CN103930518A true CN103930518A (en) 2014-07-16
CN103930518B CN103930518B (en) 2015-09-16

Family

ID=48470349

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280055332.9A Active CN103930518B (en) 2011-11-24 2012-11-23 luminescent material and forming method thereof

Country Status (5)

Country Link
US (1) US8871115B2 (en)
EP (1) EP2782976B1 (en)
JP (1) JP6033879B2 (en)
CN (1) CN103930518B (en)
WO (1) WO2013078460A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271776A (en) * 2015-11-27 2016-01-27 宁波大学 Rare-earth-ion-doped Cs2LuCl5 microcrystalline glass and preparation method thereof
CN105271777A (en) * 2015-11-27 2016-01-27 宁波大学 Rare-earth ion doped Rb2LaBr5 microcrystalline glass and preparation method thereof
CN105271769A (en) * 2015-11-27 2016-01-27 宁波大学 Rare earth ion doped K3GdI6 microcrystal glass and preparation method thereof
CN105271768A (en) * 2015-11-27 2016-01-27 宁波大学 Rare earth ion doped K2CeCl5 glass ceramic and preparation method thereof
CN105271767A (en) * 2015-11-27 2016-01-27 宁波大学 Rare earth ion-doped Rb2CeBr5 glass ceramic and preparation method thereof
CN105293924A (en) * 2015-11-27 2016-02-03 宁波大学 Rare earth ion doped Cs2NaYBr6 glass ceramic and preparation method thereof
CN105293928A (en) * 2015-11-27 2016-02-03 宁波大学 Rear earth ion-doped K2GdCl5 microcrystalline glass and preparation method thereof
CN105293921A (en) * 2015-11-27 2016-02-03 宁波大学 Rare earth ion doped K3LuCl6 glass ceramic and preparation method thereof
CN105293923A (en) * 2015-11-27 2016-02-03 宁波大学 Rare earth ion doped K3GdCl6 glass ceramic and preparation method thereof
CN109386801A (en) * 2017-08-09 2019-02-26 中国辐射防护研究院 A kind of lighting device of the no radioactive source without external energy
WO2021031135A1 (en) * 2019-08-21 2021-02-25 眉山博雅新材料有限公司 Crystals capable of simultaneously detecting neutrons and y/x-rays and preparation method thereof

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3049828A4 (en) * 2013-09-27 2017-06-07 Saint-Gobain Ceramics&Plastics, Inc. Analyzer device for compensating a scintillator and method of using the same
CN103951242B (en) * 2014-05-08 2016-09-14 宁波大学 Rare earth ion doped Cs2liLaI6devitrified glass and preparation method thereof
CN103952152A (en) * 2014-05-08 2014-07-30 兰州大学 Yellow long-lasting phosphor material and preparation method thereof
CN103951238B (en) * 2014-05-08 2016-09-14 宁波大学 Rare earth ion doped RbGd2i7devitrified glass and preparation method thereof
CN103951240B (en) * 2014-05-08 2016-09-14 宁波大学 Rare earth ion doped Cs2liLaCl6devitrified glass and preparation method thereof
CN103951259B (en) * 2014-05-08 2016-09-14 宁波大学 Rare earth ion doped BaI2devitrified glass and preparation method thereof
US10174248B2 (en) 2015-05-18 2019-01-08 General Electric Company Process for improved halide materials
US10053623B2 (en) 2016-03-30 2018-08-21 Saint-Gobain Ceramics & Plastics, Inc. Alkali halide scintillator and uses thereof
RU2660866C1 (en) * 2017-11-09 2018-07-10 Федеральное государственное бюджетное учреждение науки Физический институт им. П.Н. Лебедева Российской академии наук (ФГБУН ФИАН) Method for obtaining luminescent ceramics, luminescent ceramics and the detector of ionizing radiation
CN111453758B (en) * 2020-04-03 2021-03-30 南开大学 Rare earth-based halide perovskite material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180602B1 (en) * 1984-04-24 1989-03-01 Alternative Energy Research Centre, Inc. Infrared sensitive phosphor and method of preparing same
JP2003201473A (en) * 2001-10-31 2003-07-18 Nittetsu Mining Co Ltd Zinc oxide-silica inorganic porous fluorescent body and method of producing the same
US20040066354A1 (en) * 2001-09-12 2004-04-08 Masaki Aoki Plasma display apparatus, fluorescent material, and fluorescent material manufacturing method
US7166845B1 (en) * 2004-01-09 2007-01-23 Crystal Photonics, Incorporated Method of enhancing performance of cerium doped lutetium yttrium orthosilicate crystals and crystals produced thereby

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249552A (en) * 1963-02-19 1966-05-03 Westinghouse Electric Corp Method for processing electroluminescent phosphor
US3940347A (en) * 1972-06-21 1976-02-24 Gte Sylvania Incorporated Calcium tungstate X-ray phosphors and method for preparing same
US4857228A (en) * 1984-04-24 1989-08-15 Sunstone Inc. Phosphors and methods of preparing the same
JP2936902B2 (en) * 1992-07-17 1999-08-23 三菱マテリアル株式会社 Manufacturing method of EL fluorescent material
JPH08225782A (en) * 1994-11-02 1996-09-03 Fuji Electric Co Ltd Production of electroluminescent thin film
JP3122438B2 (en) * 1998-09-30 2001-01-09 株式会社東芝 Method for manufacturing ceramic scintillator, ceramic scintillator, scintillator block, X-ray detector, and X-ray CT imaging apparatus
JP2001064643A (en) * 1999-08-25 2001-03-13 Fuji Photo Film Co Ltd Production of rare earth-activated alkaline earth metal fluorohalide-based photostimulable phosphor
JP4096620B2 (en) * 2002-05-17 2008-06-04 松下電器産業株式会社 Method for manufacturing plasma display device
JP4140378B2 (en) * 2002-12-20 2008-08-27 松下電器産業株式会社 Method for manufacturing plasma display device
US7084403B2 (en) * 2003-10-17 2006-08-01 General Electric Company Scintillator compositions, and related processes and articles of manufacture
US7151261B2 (en) * 2004-01-09 2006-12-19 Crystal Photonics, Incorporated Method of enhancing performance of cerium doped lutetium orthosilicate crystals and crystals produced thereby
US7364620B2 (en) * 2004-10-28 2008-04-29 Saint-Gobain Ceramics & Plastics, Inc. Method of purifying alkaline-earth and alkali-earth halides for crystal growth
JP5017821B2 (en) * 2005-06-10 2012-09-05 日立化成工業株式会社 Single crystal for scintillator and method for producing the same
JP5103879B2 (en) 2006-09-20 2012-12-19 日立化成工業株式会社 Scintillator crystals and radiation detectors
JP5521273B2 (en) * 2007-06-01 2014-06-11 日立化成株式会社 Single crystal for scintillator, heat treatment method for producing single crystal for scintillator, and method for producing single crystal for scintillator
KR20090004179A (en) 2007-07-06 2009-01-12 삼성에스디아이 주식회사 Metallic compound hybridized nanophosphor layer, applications thereof and method for preparing metallic compound hybridized nanophosphor layer
US7863572B1 (en) 2007-07-17 2011-01-04 Sandia Corporation Fracture-resistant lanthanide scintillators
JP2011026547A (en) * 2009-06-29 2011-02-10 Hitachi Chem Co Ltd Single crystal for scintillator, method of heat treatment for manufacturing single crystal for scintillator, and method of manufacturing single crystal for scintillator
FR2967420B1 (en) * 2010-11-16 2014-01-17 Saint Gobain Cristaux Et Detecteurs SCINTILLATOR MATERIAL WITH LOW DELAYED LUMINESCENCE
JP6130360B2 (en) * 2011-06-06 2017-05-17 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド Scintillation crystals containing rare earth halides and radiation detection systems containing scintillation crystals

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180602B1 (en) * 1984-04-24 1989-03-01 Alternative Energy Research Centre, Inc. Infrared sensitive phosphor and method of preparing same
US20040066354A1 (en) * 2001-09-12 2004-04-08 Masaki Aoki Plasma display apparatus, fluorescent material, and fluorescent material manufacturing method
JP2003201473A (en) * 2001-10-31 2003-07-18 Nittetsu Mining Co Ltd Zinc oxide-silica inorganic porous fluorescent body and method of producing the same
US7166845B1 (en) * 2004-01-09 2007-01-23 Crystal Photonics, Incorporated Method of enhancing performance of cerium doped lutetium yttrium orthosilicate crystals and crystals produced thereby

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271776A (en) * 2015-11-27 2016-01-27 宁波大学 Rare-earth-ion-doped Cs2LuCl5 microcrystalline glass and preparation method thereof
CN105271777A (en) * 2015-11-27 2016-01-27 宁波大学 Rare-earth ion doped Rb2LaBr5 microcrystalline glass and preparation method thereof
CN105271769A (en) * 2015-11-27 2016-01-27 宁波大学 Rare earth ion doped K3GdI6 microcrystal glass and preparation method thereof
CN105271768A (en) * 2015-11-27 2016-01-27 宁波大学 Rare earth ion doped K2CeCl5 glass ceramic and preparation method thereof
CN105271767A (en) * 2015-11-27 2016-01-27 宁波大学 Rare earth ion-doped Rb2CeBr5 glass ceramic and preparation method thereof
CN105293924A (en) * 2015-11-27 2016-02-03 宁波大学 Rare earth ion doped Cs2NaYBr6 glass ceramic and preparation method thereof
CN105293928A (en) * 2015-11-27 2016-02-03 宁波大学 Rear earth ion-doped K2GdCl5 microcrystalline glass and preparation method thereof
CN105293921A (en) * 2015-11-27 2016-02-03 宁波大学 Rare earth ion doped K3LuCl6 glass ceramic and preparation method thereof
CN105293923A (en) * 2015-11-27 2016-02-03 宁波大学 Rare earth ion doped K3GdCl6 glass ceramic and preparation method thereof
CN109386801A (en) * 2017-08-09 2019-02-26 中国辐射防护研究院 A kind of lighting device of the no radioactive source without external energy
WO2021031135A1 (en) * 2019-08-21 2021-02-25 眉山博雅新材料有限公司 Crystals capable of simultaneously detecting neutrons and y/x-rays and preparation method thereof

Also Published As

Publication number Publication date
EP2782976A1 (en) 2014-10-01
JP6033879B2 (en) 2016-11-30
JP2015502423A (en) 2015-01-22
CN103930518B (en) 2015-09-16
US20130175475A1 (en) 2013-07-11
EP2782976B1 (en) 2019-11-13
EP2782976A4 (en) 2015-08-26
US8871115B2 (en) 2014-10-28
WO2013078460A1 (en) 2013-05-30

Similar Documents

Publication Publication Date Title
CN103930518B (en) luminescent material and forming method thereof
US11926777B2 (en) Scintillation compound including a rare earth element and a process of forming the same
US20130327986A1 (en) Scintillation compound including a rare earth element and a process of forming the same
EP2758489B1 (en) Scintillation compound including a rare earth element and a process of forming the same
EP3221718B1 (en) Novel thallium doped sodium, cesium or lithium iodide scintillators
US7767971B2 (en) High light yield fast scintillator
US9404036B2 (en) Alkali metal and alkali earth metal gadolinium halide scintillators
JP2009046598A (en) Single crystal material for scintillator
Zapadlík et al. Composition-engineered GSAG garnet: single-crystal host for fast scintillators
Huang et al. Optical properties of Eu2+-doped strontium borate glasses containing F− and Li+ ions
WO2018110451A1 (en) Phosphor for detecting ionizing radiation, phosphor material containing said phosphor, and inspection apparatus and diagnostic apparatus having said phosphor material
Adell et al. Radioluminescence properties under X-ray excitation of type III Ce3+-and Pr3+-doped KGd (PO3) 4 single crystals
Li et al. Scintillators
JP2018058708A (en) Novel compound and fluorescent material containing novel material, and inspection device, diagnostic device, illumination device and image display device each including fluorescent material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230803

Address after: Ohio, USA

Patentee after: Luxim Solutions LLC

Address before: Massachusetts

Patentee before: SAINT-GOBAIN CERAMICS & PLASTICS, Inc.